Gas analyzing process and apparatus



June 8, 1937.

B. MILLER Filed Jan. 4, 1953 MOTOR 1:1: i; 465 i I PUMP 2 Sheets-Sheet l [N VE N TOR BE/VdAM/N Z/LLER 1 1 A TTOR/QEY June 8, 1937. B. MILLER GAS ANALYZING PROCESS AND APPARATUS F 'iled Jan. 4, 1933 2 Sheets-Sheet 2 INVENTOR BENJAMIN MILLER A Tramp/E 2 wail RE LAY ORIFICE BLOCK AIR FILTER Patented June 8, 1937 GAS ANALYZING PROCESS AND APPARATUS Benjamin Miller, Richmond Hill, N. Y., assignor to Power Patents Company, Jersey City, N. J., i. a corporation of Maine Y Application January 4, 1933, Serial No. 650,133

' 15 Claims. (01. za -232) This invention relates to the quantitative measurement of the reactive components of gaseous mixtures such as those produced in various domestic and industrial combustion operations. It has especial utility in connection with the measurement of combustibles in, the exhaust gases from an internal combustion engine of the automotive type, which are in the form of reducing gases,produced under conditions of underven- The present invention overcomes these difliculties inherent .in the prior art methods and apparatus for combustion gas measurement, and insures the permanency of the calibration of the measuring instrument.

Among the more important objects of themesent invention are: 7

To provide iniconnection with combustion efficiency measurements based upon the controlled combustion of a'gas mixture,for making ac- 10 tilation.

Many methods are already known for the meas curate combustion efiiciency measurements inurement of the combustible components of varidependently of the rate of flow of the gases over one combustion gases following their admixture a heated element; with an additional reactant, generally in the form To provide a combustion efficiency indicator 15 of air. In such prior methods, a heated catalytic which will have a substantially permanentcalielement was disposed within a combustion cell bration throughout its period of use; 7 a located in the path of the gas mixture for com- To provide novel apparatus for measuring the.

' pleting the combustion of combustibles therein. efiiciency of a combustion operation employing- The resultant temperature increase was then a heating element in an electric circuit, in con- 20 measured electrically, generally employing a nection with which the need for current. bal- Wheatstone bridge circuit having therein the said ancing means has been eliminated; catalytic element and a potentiometer. 7 To provide in novel manner for maintaining The above methods have certain objectionable the accuracy of a combustion'efliciency measurfeatures inherent therein which interfere to some ing device independently of the presence of un- 25 extent with their satisfactory commercial use. burned hydrocarbon vapors or water vapor in the The catalytic element,usually in the form of gases being measured; a fine filament,is subject to mechanical deteri- To provide innovel manner for prolonging the oration and loss of its catalytic properties with effective life of a catalytic element associated continued use, due to such factors as the presence with a gas analyzer operating on the combus- 30 in the gas stream flowing around it of certain tion principle; and

amounts of unburned hydrocarbons and the de- To provide a novel combustion measuring inposit upon it of slight films of carbon and,under strument which is completely automatic. some conditions,or' moisture and other vapors. These and other objects will be evident from a Furthermore where the catalytic combustion review of the following specification and claims. 35 produces excessively high temperatures, partial In its broadest scope, the invention relates to a volatilization of the filament, may occur. The method and apparatus for determining the resultant deterioration of the filament acts to deamount of a fluid reagent that is equivalent to stroy the calibration of the instrument containone or more components of a unit quantity of a ing it. Obviously unless the instrument is more fluid mixture under examination. Although in 40 or less frequently recalibrated, the accuracy of the following description the fluid mixture being the readings at times may be open to question. examinedis indicated as the exhaust gases from Furthermore in view of the gradual filament dean internal combustion engine of the automotive terioration in use, it has been necessary heretotype, the invention obviously is notlimited therefore to employ a rheostat in the Wheatstone to. For-instance, the fluid mixturebeing measbridge circuit for balancing the current flowing ured may be the flue gases from a furnace, in through the combustion cell'at the beginning of which case the component to be measured may the respective tests to compensate for these be the excess oxygen in the flue-gases,-and the variations inthe electric resistance of the filareagent employed may be a combustible gas such ment. as hydrogen. 7 Another essential feature of these prior proc- In the somewhat more limited field of the esses was the need for maintaining at all times e su e ent 0f t e efficiency of StiO I a uniform flow of the gas mixture being comoperations carried out under conditions of underbusted within the catalytic'cell, since variations a o the invention involves the P p in the flowrate had an important effect upon the tion of a mixture of the gases to be analyzed resultant galvanometer readings. with air, oxygen, or other suitable combustionsupporting reagent. ,The said fluid mixture is divided into two streams which. preferably are,

equal in mass but this is not essential as long as .:the two portions are maintained in the same proportions. To one of thesaid portions of the fluid mixture is added a relatively small regulated amount of the gases to be analyzed or of a combustion-supporting fluid, as air, the amount.v

. thereof essentially being very small in comparition: 7

son to the amount previously present in the gasair mixture.

These two portions of the fluidmixture are then simultaneously passed into contact respec tively with two highly heated elements, disposed in separate but similar combustion cells. Combustion thereby; occurs" in the" respective cells,

generating heat unequally in thelatter. Visual' temperatures produced within the respective cells,

are balanced. The amount 'of the combustionsupporting'fluid present in the mixture when p the said heat balance is secured is measured by, 3. previously-calibrated device, as hereinafter will I be more fully described.

Referring now to the accompanying drawings which illustrate important features of the inven- Fig. 1 illustrates diagrammatically apparatus embodying the invention;

Fig. 2 is a rear elevation of an instrument v panel showing one form of apparatus embodying the invention; 1 Fig. 31s a front elevation of the device shown in Fig. 2, on a somewhat reduced scale;

Fig. 4--is' an elevation of of the invention;

Fig. 5 is a vertical section block; I v 1 q Fig. 6 illustrates somewhat diagrammatically still another modification of the invention; and Fig. 7 illustrates diagrammatically one feature of the invention. I

Referring more particularly to Fig. 1, numerals II, I3 designate similar hollow tubular combustion cells, having their respective lower ends connected with a mixing chamber I5, by means of the conduits I'I', I3, and 2|. The cells II, I3, have gas outlets 23, 25 at their respective upper ends. The conduit I1 has a fixed orifice 21 therethrough an orifice ,in;jand the conduit I9 has a fixed orifice 29 therein,--the orifices 21, 29 being so constructed that the rate of'gas flow through the conduits I1, I9 from. conduit 2| is identical, or is uniformlytic properties or may be catalytically inertf Examples of such metals are platinum and gold respectively. It is preferred'to use rhodium,'or

platinum, or platinum-rhodium alloys; .In the form shown in Fig. 1 these filamentsform the variable legs of a Wheatstohe bridge circuit, the

latter having therein the fixed resistancexelements 35, 31, and a galvanometer 39.

For producing a flow of the gas mixture through thecells II, I3,a pump 4I,-adapted to withdraw the combustible gases to be examined from another modification through conduit 43; and a pump 45,--adapted to draw air or othersuitable reactant from a suitable supply,-is connected with the chamber I5 through conduit 41. A, calibrated valve 48 is disposed in the conduit 41 and is adapted to adjust, the amount of air flowing to the chamber I5'during operation ofthe pump 45. e

. For supplying to thegas-air mixture flowing through cell-.I3 a small additional increment of air or its equivalent over that present in the gas-airmixture supplied to the cell I I, a conduit 49 having therein a fixed orifice 5| is 'con nected with the conduit I9 beyond the orifice 29in the latter. A pump 53 is adapted to force the small increment of air through conduit l8 from a source'of supply; In the practice of the. invention according to Fig. 1, the exhaust gases arefe-d at a constant rate to'mixing chamber I5 by pump 4|. Simultaneously air is forced into chamber I5 in regulated amount by pump 45. The resultant mixture of air and exhaust gases continuously flows from the mixing chamber to the respective conduits IT, IS, preferably in sub stantially equal amounts, through the respective orifices Z1, 29. A small additional amount of air I3 by means of the pump 53 and orifice 5|. The quantity of air added through the conduit 48 is extremelysmall compared to the maximum quantity of air which may be introduced to the system by the pump 45, and may for example pending upon the accuracy desired. The gas-air mixturesin the conduits I I, I9 then flow through .the'respective cells II, I3, where they come in contactwith the highly heated elements in the said cells, thereby eifectinglcombustion at the surface of .the elements in well 'known=manner.

The elements 3|, 33 are heated by a current flowing thereto from a battery orthe like to a temperature which insures combustion when combustibles and air are'present in the gas mix ture contacting therewith.

used. The adjustable orifice is then regulated to balance the heating conditions within the respective cells. 'Auxiliary air is then used during subsequent calibration of the instruments.

In'the event that thequantity of oxygen in the gas-air mixture leaving the mixing chamber I5 is substantially less than that requiredto combine with all of the combustibles present, then the energy liberated as heat in I3 will be greater than the energy liberated in II. The

electrical resistance of the element 33 will be greater than that of element 3|, and a current will flow through the galvanometer causing the galvanometerv needle to move to the left. 'The operator, noting this, adjusts the valve 48 to increase theflow of air to the mixing chamber.

When the quantity of oxygen in the gas-air mixture has increased until it is almost equivalent tothe combustible gas present in the mix- 'ture, the excess energy liberated in cell I3 over that liberated in cell II, will be just sufficient .to compensate for the greater rate of heat loss in the former due to the somewhat higher flow rate therethrough. The galvanometer will then come to zero. I

If the amount of air flowing past the valve 48 is still further increased, the rate of heatenbe from-.5 percent to 5. per cent thereof, de

25 is-then added to the gas mixture in the conduit ergy liberation will become the same in the cells II and I3, at whichtime the galvanometer needle will swing to the right, since the rate of heat loss from cell I3 is greater than the rate of heat loss from cell I I, because of the somewhat higher flow rate in the former.

, When the amount of auxiliary air brought in through the orifice'conduit 49 is extremely small in comparison tothe amount of air brought in through the main conduit. 21, this change in the position of the galvanometer needle occurs with a very slight change in-the adjustmentof the air-regulating valve 48. The adjustment of the flow-regulating valve 48 may. be employed. as a measure of the percentage of combustible components in the exhaust gases being examined.

Figs. 2 and 3 illustrate one form of commercial adaptation of the invention in the nature of a compact portable gas analyzer unit, the

various elements thereof being mounted within a container or box BI, preferably of sheet metal, which is provided with a handle 63 for convenience in transporting the same. The box has a hinged member 65, the outer face of which serves as an instrument panel. Apertures 61 in the wall serve for ventilation of the box.

The analyzer unit comprises an electric motor 69 mounted in rubber on a support II carried by the member 65. The motor is driven by power flowing thereto through electric conduit 13 controlled by switch I5. Operatively connected with the motor are two pairs of positive pressure ro-,

tary blowers or pumps 'II, I9; and BI, 83;the pumps of each pair being mounted as a unit in F coacting relationship. ,Both pairs of pumps are of like construction, so that one pair only need be described. Pumps I7, 19 are of well known type employing an eccentrically-mounted slotted rotor with freely slidable blades cooperating with the inner surface of the pump wall. The rotor shafts of the respective pumps are interconnected. The outlet from pump 11 is in permanent communication with the fluid inlet to pump I9 through a channel open to the atmosphere through a restricted outlet 85.

A pair of combustion cells I I, I3 are formed in a unitary cell block I4, preferably of metal, which is mounted upon the member 65. The cells have their upper ends open freely to discharge gases flowing therein. Air is drawn from outside the box SI through an opening in a member 31 forming the cover of a small filter chamber 89, adapted to be filled with cotton or the like. A conduit 9| connects the chamber 89 with the inlet of pump 11. The outlet of pump I9 is connected with the cell II through pipe 93 having therein a flow-regulating orifice or valve 95. It is also connected with the mixing chamber I5 through pipe 91 having therein a calibrated three-way flow-regulating valve 99 operated by means of a member IIlI mounted upon the front of the box. The construction of the valve 99 is such that the total amount of gas flowing through it remains substantially constant at all times, while the relative portions of the gas issuing to the chamber I5 and that issuing to the atmosphere through air outlet I03 may be varied selectively.

Aconduit I 05 and flexible tube I06 connect the source of the combustion gases to be analyzed with a, gas filter Ill! containing cottonor other suitable filtering material. A conduit I09 leads from the outlet of filter ID! to the inlet of pump 8L. The outlet from this pump is in permanent connection with the inlet of pump 83 through a passage which is in perm'anentrestricted com munication with the atmosphere through apertureIII. A conduit H3 connects the outlet of pump 83 with chamber i5. 7

In this modification one or more thermocou ples are substituted for the Wheatstone bridge circuit previously described. The analyzer construction is shown more particularly in Fig. 6, and comprises two heating coils H5, III of a heat-refractory metal. Platinum or silica-coated platinum or alloy may be used, mounted with in the respective cells II, I3. The said heating coils are arranged in series in an'electrical cir- 2 and 3, the motor is placed in operation, thereby pumping a regulated flow of filtered air to the mixing chamber past the regulating. valve 99, while at the same time the pumps 8|, 83draw a continuous sample of gas through conduit I05 and force the filtered gas at a substantially uniform regulated rate to the mixing chamber where it is mixed with the air flowing through valve 99. The mixed gases then are divided and flow in approximately equal amounts through the respective cells I I, I3.- A small additional amount of air is concurrently added to the fluid mixture flowing within cell I3 through the valve-controlled conduit 93.

The arrangement of the heating elements and the amount of heating current flowing therethrough preferably is so selected that when air alone is flowing through the respective cells, a

temperature in the range from 1400" to. 1600" F.

is maintained on the heated element, though cell. Asingle movement of the switch I5 serves both 'to operate the vmotortfi and energize the wires H5, In of the heater circuit.

.When the excess combustibles in the gas flowing to the analyzer is more than the equivalent of the air flowing to the mixing chamber through valve 99, the temperature developed in cell It will tend to be higher than that in cell II and the galvanometer needle will move to the left fromits balanced position. The operator then adjusts the valve 99 to increase the amount of air flowing to the mixing chamber I5 until sufficient air is present in the mixture to again return the galvanometer needle to the balanced posia lower temperature will be produced in cell I3 than that in cell i I, and the galvanometer needle will be unbalanced toward the right. Again by proper manipulation of the main air valve99 thus reducing the air flow to the mixing chamber, a point will be reached when the galva-v nometer again indicatesbalanced heat conditions within the cells II, I,3-at which time a reading 5 on the valve scale is made. The orifice or valve '95 in the auxiliary air line after once being adjusted, is leftundisturbed following the calibration of the analyzer.

In another form of the invention, illustrated 1O inFig. 4, an automatic direct combustion efliciency reading is secured with little or no attention on'the part of the operator or manual adjustment of the instrument during the combustion efliciency determination. 1

.15 Referring to Fig. 4, air is drawn to the inle of'the blower or pump I3I through an air filter 89. ,The said pump discharges a regulated amount of air to the mixing chamber I5, here shown as formed within a unitary orifice block I33 mount- 20 ed on a panel I34, the air fiowing-to'and within the block througha conduit I35 containing an adjustable orifice member I 31. In this modifi-.

cation the orifices 21, 29 are withinthe block I33, and a pressure-limiting device I 39 of well 25 known construction mounted on the block is conber and dry filter I I3 of known type. The filtered gas is then forced through line I41 to the chamber I5 through an orifice I49. A pressure-limiting device ,I5I similar to device I39is mounted on the block and communicates with conduit I41 d An air by-pass line I55, having therein an electrically-operated flow-regulating valve I51 1 connects the outlet of pump' I3I with the'inlet' thereof, whereby excess pressure in the air dis- 40 charge line from the pump can' be adjusted as variations may occur in the air consumption during the analysis.

The arrangement of thermocouplesand elec- 'tric heating elements preferably is the same in 45 this modification as in that shown in Figs.'2 and.

6'with the exception that the galvanometer I25 is replaced with a galvanometer relay I59 of well known construction arranged in the electric circuit with the thermocouples I23. The relay I59 is also connected in an electric circuit with a small reversing motor I6I or its equivalent, ar-

ranged and aidapted to close or open the valve I51 when-energized through lead wires I63, I65,

upon the flow of current through one or the other of the relay lead wires I61, I69.

nected with a pressure gauge I53, as for example by the line I1I. Such gauge when used preferably is mounted upon the face of the panel or 6 box member I34, and is calibrated in suitable V 'manner, as in terms of combustion efliciency. When thisfis done, direct calibration of the valve I51 is not necessary. A resistance element which mayconveniently be anelectric lamp I13 is shown I as mounted on the panel I34 where it serves for illuminating the gauge I53. The lamp is-arrangedin the heater circuit in series with the elements I I5, I I1.

In the operation of the automatic instrument 70 (Fig. 4), the movementof the needle in the galvanometer relay I59, upon the unbalancing of the heatsconditions in the respective cells II,'

I3, energizes the small motor I6I which then acts through suitable gearing to either close or 75 open the valve I51, thereby regulating the The outlet of pump I3I may, if desired, be conamount of air circulated by the pump, and controlling the pressure and flow rate in the line I35. With this apparatus it is only necessary to connect it to the source or. gas to be tested and to a source of suitable current. The apparatus automatically will adjust the valve I51 to produce a balanced heat condition-within the cells II, I3, and the'air demand can be read in terms of combustion. efilciency'upon the pressure gauge, I53, or upon a calibrated scale connected with the said valve. v

Fig. 6 illustrates somewhat diagrammatically a modification of the invention in which a small ofpgas to be examined is'drawn by pump I,

through the filter" I43 and thence is passed through orifice I49 to'the mixing chamber I in the manner previously described. A second conduit I8I having therein an orifice I83 leads from the pump to conduit. I9 adjacent the analyzer cell I3. No increment of auxiliary air is fed to either combustion cell.

Under certain conditions of gas concentratiom the combustion normally produced within the cells I I,-"I3, may be explosive, especially in instances where pure oxygen is being used for the reactive fluid. Since the invention is based on the measurement of the difference in intensity of the reactions-occurring in the cells 'I I, I3, and not upon the actual intensity,-the danger from explosive concentrations of gases may be overcome,should such become necessary-by diluting within themixing chamber I5 the mixture of air or-oxygen and the unknown gases by means of an inert gas such as nitrogen or carbon dioxide soas to reduce theconcentration of the reactants below the explosive limit. The inert or diluent gas may be. introduced into the chamber I5 through a valve-controlled conduit 200. (See Fig. 6.) While preferably the inert gas is added to thefluid mixture before'dividing it at the ori-' fices 21, 29,--it is likewise possible directly to dilute with the inert gas either the air or the'gas sample being analyzed. In the latter case his essential, however, that the instrument be calibrated' for such mixtures eontaining'inert gas.

When the waste gases being examined are very high in combustibles it is often convenient to combust all or a portion of the same by passing the gas mixture from the mixing chamber I5 through a combustion chamber, maintained at a suitable reaction temperature such as 1500-2000 following which the resultant gases, preferably after at least a partial reduction in temperature, are divided and flow through cells I I, I3.

As shown in Fig. 7, a heat-insulated combustion furnace 203 of quartz or the like is located in the conduit 2I leading from the mixing cham berof Fig. 2. The furnace 203 is provided with electric heating coil 205 connected in the aforementioned heating circuit H9. The conduit 2|, beyond the furnace 203 may be provided with heat radiating fins 201 or the equivalent if desired. v

' By burningthe combustibles in the furnace, the intensity of the reactions in the combustion cells of the resultant gas mixture may be more accurately'measured, without the possibility of ini the measurement of reactive components of fluid mixtures by" the addition of fluid reactants thereto which produce endothermic instead of exothermic reactions.

The apparatus of the invention may be adapted for operation on direct current or for universal 5 operation by using the proper motors and substituting a resistance for the transformer.

It is not essential that the heating elements within the cells H, l3, be of catalytic material. When non-catalytic heater elements are used,

the current flowing therethrough must be sufiiciently high to initiate a rapid uncatalyzed reaction between the various components of the fluid mixture, as hereinbefore indicated.

Under certain conditions the cells H, 83 may be partially or completely filled with catalytic packing material such as Hopcalite or other ac" tive oxides of like nature, which serves in place of electric heating-elements for initiating combustion in the cells I I, I3.

It will be evident that the present invention has overcome many of the difiiculties of the prior known methods and devices for measuring com- 7 bustion efiiciency by the catalytic combustion of the fluids being examined,and that changes in the electrical energy input in the heating circuit and loss of heat from the combustion cells may vary widely, so long as the conditions remain the same in both cells ll, l3. Previous to the present invention, it has been important that the amount of electric energy employed for heating the catalytic element be maintained constant and that the loss of energy from the cell by conduction and convection remain constant at a given temperature. This necessitated that the electrical supply to the cell be constant at all times,-that the ratio of air to gas be maintained constant, and that the rate of flow of the mixture to the analyzer be constant. In such prior practices a calibrated galvanometer has been used directly to measure the variations in temperature occurring within the cell. The ac curacy of the determination depended upon the galvanometers retaining its calibration, and upon freedom from deterioration of the catalytic element due to the occlusion of foreign material on its surface.

In the practice of the present invention the electrical heating supply to the cells and heat losses therefrom can vary over a wide range, since conditions are always substantially the same, or at least vary proportionately in the respective cells at all times. Furthermore, the speed of the pumps and the rate of flow of the gas mixture to the analyzer can vary substantially, since these rate changes occur simultaneously in proportional amounts in the gas streams flowing through the respective cells ll, l3 and so do not prevent the balancing of conditions within the cells. Since the galvanometer is used only to indicate a state 0 of unbalance in the cells 1 I, I3, it need not retain its calibration.

The invention is susceptible of modification within the scope of the appended claims.

I claim:

65 1. The method of measuring the concentration of a fluid reactant in a fluid mixture which comprises mixing therewith under conditions unfavorable for reaction a regulated amount of a second fluid reactive with the former, thereby form- 70 ing a fluid reactant mixture, dividing the said reactant mixture into two uniformly proportional portions, adding to one of said portions a small increment of either reactive fluid, thereafter conv currently subjecting the said fluid portions to 75 conditions producing reactions therein, measuring the difference in the intensities of the resultant reactions in the respective fluid portions, adjusting the amount of second reactive fluid in the said fluid reactant mixture to balance the intensities of the said reactions, and measuring the amount of the second reactive fluid thus required.

2. In a method of measuring the efliciency of a combustion operation by the controlled combustion of exit gases produced thereby, the steps of coxnbusting a flowing regulated mixture of said exit gases and a combustion-supporting gas, concurrently combusting a second flowing mixture containing the said exit gases and a slightly larger regulated proportion of combustion-supporting 15 gas than that present in the first-named mixture and flowing at approximately the same rate as the latter, adjusting the volume of combustionsupporting gases present in each of the said mixtures undergoing combustion to balance the tem- 20 peratures produced therein, and measuring the amount of combustion-supporting gas thus required.

3. The method of measuring the amount of a reactant in a gas mixture, which comprises mix- 25 ing with the latter under conditions unfavorable for reaction a second reactant, dividing the resultant reactant mixture into two fixed portions, adding a small fixed increment of one of the said reactants to one of the said portions, con- 30 currently reacting the respective portions in separate reaction zones, thereby producing heat of unequal intensity in the respective zones, adjusting the amount of the said second reactant required to balance the temperatures developed 5 within the said zones, and measuring the amount thereof thus required.

4. The method of measuring the efficiency of a combustion operation by the controlled combustion of waste gases produced thereby, which 40 comprises forming a regulated mixture of said gases and a combustion-supporting gas, dividing the said mixture into two uniformly proportional portions, adding a small fixed increment of a combustion element to one of the portions, con- 45 currently effecting combustion of the respective portions under similar conditions, thereby producing temperatures in the said portions, regulating the amount of combustion-supporting gas in the said mixture to balance the heat produced 50 in the respective portions, and measuring the amount of the combustion-supporting gas so required.

5. The method of measuring the efficiency of a combustion operation, which comprises mixing 55 Waste gases from such operation with a regulated amount of a combustion-supporting gas, separating the resultant mixture into two uniformly proportional portions, diluting one of the said portions With a small fixed increment of combustion-supporting gas, thereafter separately but concurrently passing the respective portions into contact with heated elements, thereby effecting combustion and generating heat in such portions, adjusting the amount of combustion-supporting gas added to the waste gases in the first-named mixing operation to produce heats of approximately equal intensity by the respective combus tions, and rneasuring'the amount of combustionsupporting gas thus required.

' 6. The, method of measuring the efficiency of an internal combustion engine of the automotive type by the controlled combustion of exhaust gases produced thereby, which comprises the steps of concurrently measuring the resistance developed the amount of air required to effect such balance.

- second fluid reactive with the former, adding.

'7. The method of measuring the concentration of a fluid reactant in a fluid mixture which comprises mixing therewith under conditions unfavorable for reaction a regulated amount of a thereto a third fluid which is inert to both of the said fluids, dividing the resulting reactant mixture into uniformly proportional portions, adding to one of the said portions a small increment of one of the reactive fluids, thereafter concurrently subjecting the said'fluid portions to conditions pro-'- ducing reactions therein, measuring the difference in the intensities ofthe resultant reactions in the respective fluid portions, adjusting the amount of the secondreactive fluid in the said reactant fluid mixture'to balance the intensities of the said reactions, and measuring the amount of the second reactive fluid thus required.

8. Themethod of measuring the extent of an incomplete chemical reaction, which comprises mixing a fluid product of the reaction with a regulated amount of a second fluid reactive with a component of thefluid product, thereby forming a uniform fluid mixture, reacting the fluid mixture under conditions substantially to reduce the amount of one of the reactive fluid components and to form a residual reaction mixture, dividing the residual reaction mixture into two uniformly proportional portions, adding to one of the said portions a small increment of one of the said reactive fluids, thereafter concurrently subjecting the said fluid portions to conditions producing reactions therein, measuringthe difference in the intensities of the last-named reactions in the respective fluid portions, adjusting the amount of second reactive fluid in the firstnamed fluid mixture to balance the intensities of the said reactions, and measuring the amount of the second reactive fluid thus required.

9.-In combination, means for continuously forming a regulated mixture of combustible gases and a combustion-supporting gas, means adapted to divide the said mixture into two uniformly proportional portions, means for modifying one of the said portions by adding thereto a small fixed increment of combustion-supporting gas, two combustion cells, means for separately conducting the respective modifled and unmodified portions to corresponding cells, a plurality of means connected in series within the respective cells and adapted when heated to produce opposing electromotive forces, means for indicating the direction of the resultant electromotive force developed in the cells, and calibrated means for regulating and measuring the combustionsupporting gas flowing to the flrstenamed mixing means. I v

10. In apparatus'for measuring the, concentration of a, reactive component of afluid,' the combination which comprises two reaction cells, means for mixing the said fluid with a regulated "amount-of a fluid reactant, means for continuously dividing the resultant mixture into two uniformly proportioned portions, means for modifying one of theportions by mixing therewith a small fixed increment of the said reactant, means directing each of the respective modified and unmodified portions through a corresponding one of the cells, means for indicating any difference in temperatures developed in the two cells, andmeans operably connected to and controlled by said temperature indicating means for controlling and metering the delivery of fluid reactant to the first named mixing means.

11. In combination, a Wheatstone bridge circuit having a source of electric potential, 9. galvanometer and two catalytic elements, a separate combustion cell enclosing each of the respective catalytic elements, mixing means for continuously forming a regulated mixture of a gas being examined for combustible and a combustion-supporting gas, means for regulating and measuring the supply of combustion-supporting gas to said mixing means, means for separating the said mixture into two uniformly proportional portions,

means for adding to one of the said portions a small fixed increment of combustion-supporting gas,and means for concurrently flowing the said portions through the corresponding cells.

12. In apparatus for measuring the concentration of a reactive component of a fluid, the combination which comprises two reaction cells, heating means within the cells, means for'mixing the said fluid with a regulated amount of a fluid reactant, means for continuously separating the resultant mixture into constantly proportional portions, means for mixing with one .of the portions a small fixed increment of the said reactant, means directing each of the respective portions through a corresponding one of the cells, inter! connected means in the said cells for producing an electromotive force dependent upon the resultant of the temperatures developed in the respective cells, and automatic means operatively connected to'the last named means and operatively responsive to the resultant electromotive force produced thereby, for controlling and measuring the delivery of the fluid reactant to the first named mixing means.

1 3. The method of measuring the concentration of a fluid reactant in a fluid mixture which comprises mixing therewith under conditions unfavorable for reaction a regulated amount of a second fluid reactive with the former,- dividing the resulting reaction mixture into two uniformly proportional portions, adding to one of said portions a small fixed increment of a fluid reactive with one of said first named fluids, there- ,14. In'apparatus for measuring the amount of a combustion element in a fluid, the combination of mixing means for mixing with said fluida second fluid combustion element reactive with the former, means for dividing the resulting mixtu e,

into two uniformly proportional portions, a device for modifying one of the said portions by introducingthereto. a small fixed increment of a combustion element adapted to react with one of said first named combustion elements, means for regulating and measuring the second combustion element flowing to the first named mixing means, two reaction cells, means for directing the said modified portion through one cell, means for directing the unmodified portion through the other ceIL'and means for indicating any difference in temperatures developed in the two cells.

15. The method of measuring the concentration of a combustion element in a fluid which comprises, mixing therewith a measured amount of a second element of combustion reactive with said first element under conditions different than those obtaining when the elements are mixed, dividing said mixture into two uniformly proportional portions, adding to one of said portions a small increment of a combustion element, concurrently efiecting combustion of the respective portions under similar conditions thereby producing heat in the said portions, regulating the amount of the second element of combustion in the said mixture to balance the temperatures produced in the respective portions, and measuring the amount of the second element of combustion so required.

BENJAMIN MILLER. 

